Hierarchical NiCo2O4 microspheres assembled by nanorods with p-type response for detection of triethylamine

The morphological and structural design provides an efficient protocol to optimize the performance of gas sensing materials. In this work, a gas sensor with high sensitivity for triethylamine (TEA) detection is developed based on p-type NiCo₂O₄ hierarchical microspheres. The NiCo₂O₄ microspheres, synthesized by a hydrothermal route, have a three-dimensional (3D) urchin-like structure assembled by nanorod building blocks. The structure-property correlation has been investigated by powder X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscope, scanning electron microscope, N₂ adsorption-desorption tests and comprehensive gas sensing experiments. The influence of calcination temperature on the morphological structure and sensing performances has been investigated. Results reveal that the material annealed at 300 °C has a very large specific surface area of 125.27 m²/g, thereby demonstrating the best TEA sensing properties including high response and low limit of detection (145 ppb), good selectivity and stability. The further increase of the calcination temperature leads to the collapse of the 3D hierarchical structure with significantly decreased surface area, which is found to decline the sensing performances. This work indicates the promise of ternary p-type metal oxide nanostructures for application in highly sensitive gas sensors.     

Fabrication of high sensitivity 2-PEA sensor based on Aldehyde-functionalized mesoporous carbon

2-Phenylethylamine (2-PEA) is one of the main ingredients for stimulants. Therefore, it is necessary to limit its use and illegal trade by conveniently detecting 2-PEA vapour. Here, a QCM based 2-PEA gas sensor was constructed by using aldehyde functionalized mesoporous carbon (FDU-15-CHO) as sensing materials designed according to Schiff base adsorption role. The 2D hexagonal mesoporous structures of the sensing material have been confirmed by small-angle X-ray diffraction (SXRD), transmission electron microscopy (TEM), and N₂ adsorption-desorption isotherms. The covalent grafting of aldehyde group onto the FDU-15 was confirmed by Fourier transform infrared spectroscopy (FT-IR). FDU-15-CHO based Quartz Crystal Microbalance (QCM) sensor shows better sensitivity to 2-PEA than its parent FDU-15. Besides, the detection limit of FDU-15-CHO based sensor can reach down to 1 ppm, and its selectivity and reproducibility are satisfactory. The high concentrations of active sites in the mesopores of FDU-15 are believed to facilitate 2-PEA adsorption, and thus the presence of the -CHO group leading to sensitive and selective response, which is verified by Gaussian simulation     

金属有机框架及其衍生的金属氧化物在电阻式气体传感器中的应用

高灵敏和选择性的气体传感器对于实时监测大气中有毒有害气体和早期的疾病诊断具有重要的意义。目前,传统的气敏材料仍然存在着许多问题亟待解决,例如：选择性差、检测极限不够低、使用寿命短等。作为一种多孔的配位聚合物,金属有机框架材料(MOFs)由于其超高的比表面积和较大的孔隙率在气体传感器领域已经得到广泛的应用。利用MOFs自身或者由它们衍生的不同纳米结构的金属氧化物可以提升气体传感器的灵敏度和选择性,为制备新型高性能的气体传感器提供了新的思路和方向。本文结合金属氧化物半导体(MOS)的气敏机理,综述了不同结构的MOFs及其衍生的金属氧化物在电阻式气体传感器领域的研究进展,并对其应用前景和发展方向作出了展望。     

High-Performance Sensor Based on Thin-Film Metallic Glass/Ultra-nanocrystalline Diamond/ZnO Nanorod Heterostructures for Detection of Hydrogen Gas at Room Temperature

This article outlines a novel material to enable the detection of hydrogen gas. The material combines thin-film metallic glass (TFMG), ultra-nanocrystalline diamond (UNCD), and ZnO nanorods (ZNRs) and can be used as a device for effective hydrogen gas sensing. Three sensors were fabricated by using combinations of pure ZNRs (Z), UNCD/ZNRs (DZ), and TFMG/UNCD/ZNRs (MDZ). The MDZ device exhibited a performance superior to the other configurations, with a sensing response of 34 % under very low hydrogen gas concentrations (10 ppm) at room temperature. Remarkably, the MDZ-based sensor exhibits an ultra-high sensitivity of 60.5 % under 500 ppm H₂. The MDZ sensor proved very fast in terms of response time (20 s) and recovery time (35 s). In terms of selectivity, the sensors were particularly suited to hydrogen gas. The sensor achieved the same response performance even after two months, thereby demonstrating the superior stability. It is postulated that the superior performance of MDZ can be attributed to defect-related adsorption as well as charge carrier density. This paper also discusses the respective energy band models of these heterostructures and also the interface effect on the gas sensing enhancements. The results indicate that the proposed hybrid TFMG/UNCD/ZNRs nanostructures could be utilized as high-performance hydrogen gas sensors.     

WO3/TiO2 复合纤维的制备及储能光催化性能

以钛酸正丁酯为前驱体, 采用静电纺丝技术制得了纯锐钛矿TiO2纤维, 并以其为基质, 通过水热法制备了具有异质结构的WO3/TiO2复合纤维. 利用X射线衍射仪(XRD)、 扫描电子显微镜(SEM)、 能量色散光谱仪(EDS)、 透射电子显微镜(TEM)和高分辨透射电子显微镜(HRTEM)等对样品的结构和形貌进行了表征. 以罗丹明B的脱色降解为模型反应, 考察了样品的光催化性能和储能光催化性能. 结果表明, 花状WO3微球包裹在TiO2纤维上, 得到了具有异质结构的WO3/TiO2复合纤维光催化剂. WO3与TiO2复合有利于光生载流子的输运和分离, 增强了体系的量子效率, 提高了光催化活性. WO3/TiO2 复合纤维经光照处理后, 在黑暗条件下显示出储能光催化特性.     

Evaluation of electrodeposited gold nanostructures for applications in QCM sensing

The electrodeposition of gold nanostructures increases the surface area of a biosensor, which brings an enhancement of the sensitivity by increasing the amount of analyte binding to the surface. To evaluate the relationship among the surface structure, the area and the analyte binding, we quantitatively analyzed them for quartz crystal microbalance (QCM) sensing by scanning electron microscopy and cyclic voltammetry measurements. The results indicate a several-times increase of analyte bindings, and also the limitation of the sensing performance.     

High ethanol sensitivity of Palladium/TiO2 nanobelt surface heterostructures dominated by enlarged surface area and nano-Schottky junctions

TiO₂ nanobelts were prepared by the hydrothermal growth method. The surface of the nanobelts was coarsened by selective acid corrosion and functionalized with Pd catalyst particles. Three nanobelt samples (TiO₂ nanobelts, surface-coarsened TiO₂ nanobelts and Pd nanoparticle/TiO₂ nanobelt surface heterostructures) were configured as gas sensors and their sensing ability was measured. Both the surface-coarsened nanobelts and the Pd nanoparticle-decorated TiO₂ nanobelts exhibited dramatically improved sensitivity to ethanol vapor. Pd nanoparticle-decorated TiO₂ nanobelts with surface heterostructures exhibited the best sensitivity, selectivity, working temperature, response/recovery time, and reproducibility. The excellent ethanol sensing performance is attributed to the large surface area and enhancement by Schottky barrier-type junctions between the Pd nanoparticles and TiO₂ nanobelts.     

H2S Dosimetry by CuO: Towards Stable Sensors by Unravelling the Underlying Solid-State Chemistry

The precise detection of the toxic gas H₂S requires reliable sensitivity and specificity of sensors even at minute concentrations of as low as 10 ppm, the value corresponding to typical exposure limits. CuO can be used for H₂S dosimetry, based on the formation of conductive CuS and the concomitant significant increase in conductance. In theory, at elevated temperature the reaction is reversed and CuO is formed, ideally enabling repeated and long-term use of one sensor. Yet, the performance of CuO tends to drop upon cycling. Utilizing defined CuO nanorods we thoroughly elucidated the associated detrimental chemical changes directly on the sensors, by Raman and electron microscopy analysis of each step during sensing (CuO→CuS) and regeneration (CuS→CuO) cycles. We find the decrease in the sensing performance is mainly caused by the irreversible formation of CuSO₄ during regeneration. The findings allowed us to develop strategies to reduce CuSO₄ formation and thus to substantially maintain the sensing stability even for repeated cycles. We achieved CuO-based dosimeters possessing a response time of a few minutes only, even for 10 ppm H₂S, and prolonged life-time.     

Investigation of QCM Sensors with Azobenzene Functionalized Coatings for the Detection of Nitroaromatics

Quartz Crystal Microbalance (QCM) based sensors have been used extensively to detect trace amounts of organic chemical vapors. These devices typically incorporate a polymer coating as an active layer that can bind the analytes of interest. Analyte adsorption causes a shift in the resonant frequency of the device proportional to the amount of adsorbed material. Currently some of the polymer coatings used in these sensors utilize hydrogen bonding to adsorb analytes. Dipole-dipole type interactions can also be utilized to promote interaction of the analytes with the polymer coating. Polymer coating containing segments that have a permanent molecular dipole can interact with explosive taggants. In this study, novel polypropylene glycol based polymers that incorporate both hydrogen bonding moieties and segments having large permanent dipole moment (p-nitroazobenzene functional groups) were synthesized and tested. The precursor polymer was prepared by the polymerization of the diglycidyl ether end functionalized polypropylene glycol macromer and aniline. The precursor polymers were post functionalized by an azo-coupling reaction. The sensor response to saturated vapors of o-nitrotoluene, nitrobenzene and 2,4 dinitrotoluene (DNT) saturated vapors was evaluated. Incorporation of p-nitroazobenzene moieties in the polymer increased the sensitivity of detection of the analytes. These studies offer new possibilities for using combination of interactions to improve the sensitivity of the QCM based sensors in the detection of nitroaromatic materials.     

Morphology‐Dependent Gas‐Sensing Properties of ZnO Nanostructures for Chlorophenol

The crystal‐plane effect of ZnO nanostructures on the toxic 2‐chlorophenol gas‐sensing properties was examined. Three kinds of single‐crystalline ZnO nanostructures including nanoawls, nanorods, and nanodisks were synthesized by using different capping agents via simple hydrothermal routes. Different crystal surfaces were expected for these ZnO nanostructures. The sensing tests results showed that ZnO nanodisks exhibited the greatest sensitivity for the detection of toxic 2‐chlorophenol. The results revealed that the sensitivity of these ZnO samples was heavily dependent on their exposed surfaces. The polar (0001) planes were most reactive and could be considered as the critical factor for the gas‐sensing performance. In addition, calculations using density functional theory were employed to simulate the gas‐sensing reaction involving surface reconstruction and charge transfer both of which result in the change of electronic conductance of ZnO.     

Electrochemical Properties of Highly Sensitive and Selective CuO Nanostructures Based Neurotransmitter Dopamine Sensor

In this article, electrochemical properties of CuO nanostructures based dopamine (DA) sensor was investigated. The morphology, structure, optical, and compositional properties of the CuO nanostructures were characterized by using SEM, XRD, UV‐Vis, and XPS techniques. The electrochemical properties were investigated using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) techniques. The CV results indicate that biosensors based on CuO nanostructures exhibit a high selectivity and sensitivity of 0.1975 μA μM^–1 toward DA and effectively avoids the interference of ascorbic acid (AA) and uric acid (UA). The obtained EIS spectra for CuO sensors were analysed using an electrical equivalent circuit to understand the bulk and surface response via the capacitive and resistive parameters. The EIS measurement also leads to the direct determination of parameters like series resistance and ion diffusion phenomena at electrode‐electrolyte interface. The experimental CV and EIS results along with their analysis will have a significant impact on understanding the mechanism of high sensitivity and selectivity performance of CuO based sensors. This study may also lay the basis for efficient characterization of biosensors by coupling both the CV and EIS characterization techniques.     

Preparation of polythiophene/WO_3 organic-inorganic hybrids and their gas sensing properties for NO_2 detection at low temperature

Polythiophene/WO3(PTP/WO3)organic-inorganic hybrids were synthesized by an in situ chemical oxidative polymerization method,and char- acterized by X-ray diffraction(XRD),transmission electron microscopy(TEM)and thermo-gravimetric analysis(TGA).The Polythiophene/ WO3 hybrids have higher thermal stability than pure polythiophene,which is beneficial to potential application as chemical sensors.Gas sensing measurements demonstrate that the gas sensor based on the Polythiophene/WO3 hybrids has high response and good selectivity for de- tecting NO2 of ppm level at low temperature.Both the operating temperature and PTP contents have an influence on the response of PTP/WO3 hybrids to NO2.The 10 wt%PTP/WO3 hybrid showed the highest response at low operating temperature of 70-C.It is expected that the PTP/WO3 hybrids can be potentially used as gas sensor material for detecting the low concentration of NO2 at low temperature.     

Electrochemical behavior and voltammetric determination of paracetamol on Nafion/TiO2-graphene modified glassy carbon electrode

A simple and sensitive method was developed for the detection of mercury ions with quartz crystal microbalance (QCM), based on the specific thymine-Hg(2+)-thymine (T-Hg(2+)-T) interaction and gold nanoparticle-mediated signal amplification. To enhance the sensitivity of detection a sandwich hybridization approach was adopted in this work. The QCM gold surface was modified with the probe SH-oligonucleotides (Oligo-1) and 6-Mercapto-1-hexanol to form an active surface for the hybridization of a longer ss-DNA (Oligo-2), and then Oligo-3 hybridazated with an excess and matching part of Oligo-2. In all oligonucleotides, there existed T bases. In the presence of Hg(2+) ions, special T-Hg(2+)-T reaction greatly enhanced the hybridization of oligonucleotides and detection sensitivity. The gold nanoparticle (Au NPs) amplifier method further increased the sensitivity of detection. A detection sensitivity of 5nM Hg(2+) was obtained in the QCM system, whereas other coexisting metal ions (such as Ni(2+), Mg(2+), Co(2+), Cr(3+), Pb(2+), Cd(2+), Mn(2+), Ba(2+)) had no significant interference. This method reveals a new approach for the manufacture of a kind of simple and low cost sensors for the Hg(2+) detection.     

Carnation‐like CuO Hierarchical Nanostructures Assembled by Porous Nanosheets for Nonenzymatic Glucose Sensing

Carnation‐like CuO hierarchical nanostructures assembled by ultrathin porous nanosheets were successfully fabricated via a facile solvothermal route followed with heat treatment. As‐prepared CuO nanostructures exhibited excellent catalytic activity toward glucose oxidation in the absence of any enzymes. Under the optimized conditions, the CuO‐based enzymeless glucose sensor showed high sensitivity of 3.15 mA mM^?1 cm^?2, low limit of detection (98 nM, S/N=3), good reproducibility, excellent selectivity and long‐time stability. The superb nonenzymatic glucose sensing performance of the CuO hierarchical nanostructures was attributed to the highly catalytically active sites at the edges and basal planes of the CuO nanosheets, facile transportation of analytes through the abundant mesopores and macropores, robust and stable hierarchical structure. Moreover, the CuO‐based enzymeless glucose sensor showed high accuracy and reliability in comparison with clinical glucometer for quantitative determination of glucose in human blood serum samples.     

MIL-125(Ti)及其氨基功能化材料修饰石英晶体微天平的湿敏性能

采用简单的溶剂热法制备金属有机框架化合物MIL-125(Ti)和NH_2-MIL-125(Ti)材料,并通过X射线衍射仪、扫描电子显微镜、傅氏转换红外线光谱分析仪和比表面积测试仪对所得样品进行表征。将2种材料修饰构建为石英晶体微天平传感器,测试其在11%～97%RH相对湿度范围内的湿度感测性能。实验结果表明,基于MIL-125(Ti)和NH_2-MIL-125(Ti)构建的传感器对湿度具有灵敏度高、重复性好、响应/恢复快等特点。相对于没有氨基修饰的MIL-125(Ti),NH_2-MIL-125(Ti)材料修饰的传感器对湿度表现出更高的响应性能。在环境湿度约52%时,NH_2-MIL-125(Ti)传感器对11%RH湿度响应值比MIL-125(Ti)湿度传感器的大57 Hz,说明氨基功能化对MIL-125(Ti)的湿敏性能有显著的增强作用。此外,通过Materials Studio模拟计算获得了水分子与MIL-125(Ti)及NH_2-MIL-125(Ti)作用的吸附焓,也证明氨基功能化对MIL-125(Ti)的湿度敏感性能具有增强作用。     

不同形貌WO3的水热合成及其在水处理中的应用研究

三氧化钨(WO₃)以其较窄的带隙,成为继二氧化钛(TiO₂)之后颇具发展潜力的n型半导体光催化剂.本文采用水热合成法,通过调控反应参数,如原料组成、沉淀时间等,合成了不同形貌和晶型的WO₃;采用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、傅里叶变换红外光谱(FT-IR)、氮气吸附-脱附(N₂ adsorption-desorption)等表征了所合成的WO₃产品,发现原料组成、沉淀时间等条件对WO₃的晶型和形貌都有影响;研究了所合成的WO₃产品去除水中亚甲基蓝染料污染物的性能,结果表明,所制备的WO₃对水中亚甲基蓝具有较好的去除效果,去除率可达97%.     

Plasmonic properties of silver nanostructures coated with an amorphous silicon-carbon alloy and their applications for sensitive sensing of DNA hybridization

The use of an amorphous silicon-carbon alloy overcoating on silver nanostructures in a localized surface plasmon resonance (LSPR) sensing platform allows for decreasing the detection limit by an order of magnitude as compared to sensors based on gold nanostructures deposited on glass. In addition, silver based multilayer structures show a distinct plasmonic behaviour as compared to gold based nanostructures, which provides the sensor with an increased short-range sensitivity and a decreased long-range sensitivity.     

桥连氧化钨纳米线的可控合成及气敏性质

The rapid development of industrialization has resulted in severe environmental problems. A comprehensive assessment of air quality is urgently required all around the world. Among various technologies used in gas molecule detection, including Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy, mass spectroscopy (MS), electrochemical sensors, and metal oxide semiconductor (MOS) gas sensors, MOS gas sensors possess the advantages of small dimension, low power consumption, high sensitivity, low production cost, and excellent silicon chip compatibility. MOS sensors hold great promise for future Internet of Things (IoT) sensors, which will have a profound impact on indoor and outdoor air quality monitoring. The development of nanotechnology has significantly enhanced the development of MOS gas sensors. Among various nanostructures like nanoparticles, nanosheets and nanowires, the emergence of quasi-one-dimensional (q1D) nanowires/nanorods/nanofibers, with unique q1D geometry (facilitating fast carrier transport) and large surface-to-volume ratio, potentially act as ideal sensing channels for MOS sensors with extremely small dimension, and good stability and sensitivity. These structures have thus been the focus of extensive research. Among the various MOS nanomaterials available, tungsten oxide (WO_3-x, 0 ≤ x < 1) nanowires feature the characteristic properties (multiple oxidation states, rich substoichiometric oxides with distinct properties, photo/electrochromism, (photo)catalytic properties, etc.), and unique q1D geometry (single-crystalline pathway for fast carrier transport, large surface-to-volume ratio, etc.). WO_3-x nanowires have broad applications in smart windows, energy conversation & storage, and gas sensing devices, and have thus become a focus of attention. In this paper, the fundamental properties of tungsten oxide, synthesis methods and growth mechanism of tungsten oxide nanowires are reviewed. Among various (vapor-liquid-solid (VLS), vapor-solid (VS) and thermal oxidation) growth methods, the thermal oxidation method enables an in situ integration of WO_3-x nanowires on predefined electrodes (so-called bridged nanowire devices) via the oxidation of lithographically patterned W film at relatively low growth temperature (~500 ℃) because of interfacial strain, defects and oxygen on the surface of the W film. The novel bridged nanowire-based sensor devices outperform traditional lateral nanowire devices in terms of larger exposure area, low power consumption via self-heating, and greater convenience in device processing. Recent progress in bridged WO_3-x nanowire devices and sensitive NO_x molecule detection under low power consumption have also been reviewed. Power consumption of as low as a few milliwatts was achieved, and the detection limit of NO₂ was reduced to 0.3 ppb (1 ppb = 1 × 10^-9, volume fraction). In situ formed bridged WO_3-x nanowire devices potentially satisfy the strict requirements of IoT sensors (small dimension, low power consumption, high integration, low cost, high sensitivity, and selectivity), and hold great promises for future IoT sensors.     

Surface engineering of one-dimensional tin oxide nanostructures for chemical sensors

Nanostructured materials are promising candidates for chemical sensors due to their fascinating physicochemical properties. Among various candidates, tin oxide (SnO₂) has been widely explored in gas sensing elements due to its excellent chemical stability, low cost, ease of fabrication and remarkable reproducibility. We are presenting an overview on recent investigations on 1-dimensional (1D) SnO₂ nanostructures for chemical sensing. In particular, we focus on the performance of devices based on surface engineered SnO₂ nanostructures, and on aspects of morphology, size, and functionality. The synthesis and sensing mechanism of highly selective, sensitive and stable 1D nanostructures for use in chemical sensing are discussed first. This is followed by a discussion of the relationship between the surface properties of the SnO₂ layer and the sensor performance from a thermodynamic point of view. Then, the opportunities and recent progress of chemical sensors fabricated from 1D SnO₂ heterogeneous nanostructures are discussed. Finally, we summarize current challenges in terms of improving the performance of chemical (gas) sensors using such nanostructures and suggest potential applications. Contains 101 references.

Acoustic Wave Mass Sensors

The application of acoustic wave microsensors for mass sensing will be reviewed with focus on the quartz crystal microbalance (QCM) and surface acoustic wave (SAW) devices. The use of QCM and SAW devices in chemical sensing as well as in the determination of solid and liquid properties will be described. In chemical sensing, it is unlikely that a single sensor with a single coating will display a selective and reversible response to a given analyte in a mixture. Alternative strategies such as the use of sensor arrays and the use of sampling devices can be used to improve performance. QCM sensors (QCMs) will oscillate under liquids; their use in under-liquid sensing will be discussed. This revised version was published online in July 2006 with corrections to the Cover Date.